KR810000009B1 - Fire retardant intumescent putty - Google Patents

Abstract

The title compns., with low air permeability and having cone penetration value(JIS A 5752-1966, 5S, 20≰C) 2-40mm/150g, contain 4% org. substance, semisolid or fluid at room temp., with viscosity 50-100,000 cst at 99≰C, and >=13% amine phosphate[I; O<X/Y<=3 and n = 1-14 .

Description

Foam fire putty

1 is a triangular coordinate showing the component ratios of (b), (c) and (d) in a preferred embodiment of the present invention.

TECHNICAL FIELD The present invention relates to a foamable fireproof putty having excellent fire protection and flame retardant function.

In recent years, miserable cases of building fires caused by the smoke or combustion of various kinds of synthetic polymer interior materials, rubber, and plastic wire cables have been frequently reported.

For this reason, fire protection measures are urgently emphasized these days, such as the strengthening of the law on arson, and the development of technology on arson has become a very minor problem among related parties.

Today, fireproofing materials, flame retardant materials, and the like are used for interior materials of buildings, ships, vehicles, etc., and fire protection measures such as protecting emergency facilities with firewalls have been taken. However, when these interior materials themselves are also exposed to high heat, they may deform or carbonize, creating gaps in them, causing flames to enter, speeding up heat transfer on the back, and causing fire to expand. In addition, smoke or flame may leak through the air spaces of the firewall penetrating wires, resulting in damage to the emergency equipment. By the way, as a method of fire prevention and a smoke-retardation of this kind of penetration part, methods, such as a non-flammable plate | plate material, the shielding by a block, and the filling of a nonflammable fiber, have been used conventionally. However, such a conventional method was not necessarily satisfactory in the effects of fire prevention and smoke prevention. In order to make fire prevention and flame retardance perfect, the space | gap of a penetration part may be filled with concrete at times, However, when adding a cable as such a method, the inconvenience that a concrete must be destroyed comes.

The present invention shows high airtightness and flammability by filling and filling various voids and ion spots, and when it is heated by flame, it foams itself and foamed carbonized layer. To provide a novel foamable fireproof putty exhibiting excellent fire protection by means of a two-layer, wherein the putty is (a) a liquid or semi-solid at room temperature of at least 4% by weight and a viscosity of It consists of 100,000cst organic substance and (b) at least 13% by weight nitrogen-containing phosphate compound, and conical penetration furnace (mm / 150g, 5 seconds, 20 ℃) specified in JIS A5752-1966 is 2-40 It features.

As the organic substance as the component (a) of the present invention, a semi-solid or liquid phase is exhibited at room temperature (about 20 ° C) and a viscosity of 50-100,000 cst at 210 ° F is used.

The semi-solid phase means that the cone penetration value (Cone Penetration Value) measured by JIS k2560-1969 (Testing method for cone penetration of labricating Greases) is 50 or more. When the viscosity at 210 ° F. as the component (a) is outside the range described above, an excellent putty of fire prevention and natural performance for the purpose of the present invention cannot be obtained. And it is preferable to have 200-50,000cst, especially 500-10,000cst at this temperature. Component (a) is chemically composed of 0 to 6 elements other than hydrogen, such as O, N, halogens, P, S, per 10 carbon atoms, preferably O, N, halogens, P It is an organic compound containing 1-5. Specific examples of the component (a) include low to medium polymers of olefins such as petroleum hydrocarbon oil, butene, propylene and ethylene, polyalkylene glycol oil and chlorinated paraffin. And halogenated base materials such as canceled epoxy chlorinated diphenyl and chlorinated triphenyl, rubber polymers such as chloroprene, butadiene and nitrile, and polymers such as urethane oligomers and asphalts or mixtures of two or more thereof. As mixtures of solid natural or synthetic polymers with organic materials at room temperature, those meeting the above requirements are also used. Examples of such a mixture include polymer materials such as ethylene vinyl acetate copolymer, natural rubber, styrene butadiene rubber, nitrile rubber, chloroprene rubber, polyisobutylene, atactic poly propylene or asphalt, paraffin wax, And waxes such as microcrystalline wax and Fisher-Tropsch wax, modified alkyd resins, rosin, and the like at room temperature, and mixtures with the organic materials exemplified above.

It is a substance which does not contain Si further as a (a) component.

The nitrogen-containing phosphorylated compound of component (b) of the present invention is a general formula

One or all of the hydrogen of phosphoric acid represented by the above is substituted by the nitrogen-containing group described below, and the content of phosphoric acid is at least 7% by weight, preferably at least 10% by weight.

The said nitrogen-containing group consists of hydrogen, carbon, or they couple | bonded with nitrogen. For example, such a group may be a combination of NH ', NH ₂ =, NH _3- , NH _4- , -NC-, or a plurality of such groups in a cyclic or chain form. Examples of the nitrogen-containing phosphate compound include ammonium phosphates such as monoammonium phosphate, diammonium phosphate, ammonium polyphosphate, (average molecular weight 200-300,000, content 10-25% by weight), melamine monophosphate, melamine diphosphate, melamine triphosphate Phosphate amines such as phosphate amides such as guanyl urea phosphate, urea phosphate, polyphosphorylamide, and phosphotritrianilide. Among these, melamine monophosphate and ammonium polyphosphate are preferred.

The average degree of polymerization of 20-400, represented by the general formula H (nm) ₊₂ (NH ₄ ) mPnO ₃ n ₊₁ (n / m = 0.7-1.1), or

General formula

In the present invention, the average polymerization degree represented by (NH ₄ ) n ₊₂ Pn O ₃ n ₊₁ may be used as a mixture of two or more of these.

In the putty of the present invention comprising the component (a) and the component (b), the component (a) needs to contain at least 4% (weight, the following). Less than that is the lack of confidentiality and flammability. Therefore, the component (a) is preferably at least 5%, particularly at least 15% or more. On the other hand, it is necessary to contain at least 13% of (b) component. If less than that, it becomes difficult to form a foamed carbonized layer even when heated by a flame. Therefore, the component (b) is at least 15%, more preferably at least 20%.

Putty of the present invention is essential to have the above chemical composition and to have a flue defined by JISA 5752-66 (putty for Metol Sash Glazing) of 2-40 mm / 150 g, 5 seconds, and 20 ° C. Shall be. If it is out of the above-mentioned range, construction workability is poor at less than 2, and more than 40 has the disadvantage of deteriorating airtightness and fire resistance. And it is preferred that the year is 3-20, especially 4-15.

Particular preference is given to a putty consisting of a 210 ° F. viscosity of 1000-10,000, 100 parts by weight of polybutene and 300-600 parts by weight of the polyammonium phosphate or melamine phosphate.

In the present invention, in addition to the components (a) and (b), when one or two or more components of the components (c) to (g) shown below coexist, further excellent in fire resistance and flame retardant performance Putty is obtained. (c) Component-hydrocarbon polyhydric alcohols: one or two or more of the OH index represented by the following formula is 0.2 or more, preferably 0.8 or more, and the carbon content of 35-70% by weight. do.

Examples of such are monopentaerythritol, dipentaerythritol, dipentaerythritol, tripentaerythritol, triethylene glycol, sorbitol, resorcinol, polypentaerythritol , Glycerin trimetholol methane, trimetholol propane, diethylene glycol, propylene glycol, hexamethylene glycol, inositool, and the like. Examples of carbohydrate compounds include dextrin, starch glucose (glucose), and sucrose ( sucrose). Preferred among these are monopentaerythritol and dipentaerythritol, tripentaerythritol and starch.

The component (c) is used in an amount of 10-150 parts, preferably 30-100 parts, and particularly 40-60 parts, per 100 parts (in weight, equal to or less) of the total nitrogen-containing phosphorylation. The use of the above components results in a putty having excellent foam fire protection.

(d) Component-foaming agents, which have a decomposition temperature of 120-400 ° C. which thermally decomposes to release nitrogen gas, carbon monoxide, carbon dioxide gas, ammonia gas, etc .;

For example, melamine resin, guanidine, which is a semi-crosslinked or fully crosslinked melamine resin at room temperature, obtained by addition condensation reaction of melamine, urea formaldehyde, aminoacetic acid, trimetholmelamine, hexametholmelamine, melamine and formaldehyde Organic amines such as dimethyl amide, butylurea, polyamide resin, casein, azodicarbonamide, nitrososulfonamide, chlorinated paraffin, parachloromethacyrenol and tetra Halogenated organic compounds such as chlorophthalic acid resin, pentachlorophenyl, glyceryl ether, sulfonhydrides such as benzene sulfonhydride, and guanyl compounds such as aminoguanyurea.

Of these, preferred are melamine, trimetholol melamine, hexamethyrolol melamine, dicyandiamide and the like. Particularly preferred is fine powder melamine that passes through at least 95% of the 300 mesh sieve. In the present invention, one kind or two or more kinds thereof are used.

The component (a) is 10-200 parts, preferably 30-150 parts, particularly 60-120 parts, per 100 parts of the nitrogen-containing phosphate compound.

The use of the component (d) results in the formation of a foamed carbonized layer having a larger thermal insulation effect, thereby further increasing the fire resistance.

(e) component-greases; Greases used in the present invention are viscous pastes or semi-solids at room temperature, in which an extender is dispersed in a natural or synthetic dispersion medium, usually in oil-based lubricating oil. Correspondingly, one kind or two or more kinds known as lubricating greases or simply greases are used. Examples of the dispersion medium include petroleum liquid lubricating oils such as trans oil, spindle oil, cable insulating oil and machine oil, rosin oil, castor oil, olive oil and light oil. Natural oils, such as polybutene oil, synthetic lubricating oils, such as chlorinated paraffin, polyethyleneglycol, etc. are used.

Examples of the extender include metal soaps such as Ba, Sr, Zn, Pb, Cd, K, Na, Ca, Li, Al, and higher fatty acid salts of metals such as non-soaps, such as bentonite ( Bentonite), silica gel (Silicagal), and phthalocyanine (Phthalocyanine).

Specific examples of the grease include sodium soap grease, calcium soap grease, lithium soap grease, aluminum complex grease and barium soap grease described in US Pat. No. 2768138, and bentonite grease, silica gel grease and the like. have.

Among the other greases, the penetration (mm / 10) measured by JISK 2560-1969 (Testing method for cone penetration of lubricating grease) is 40-500, and the penetration is 80-350. Phosphorus lithium soap grease, aluminum complex grease, bentonite grease and silica gel grease are preferable.

The usage-amount of (e) component is 70-400 parts per 100 parts of organic substance which is said (a) component, Preferably it is 100-300 parts, Especially 150-250 parts are preferable.

When the (e) component is used, there is an advantage that the putty is not melted at high temperatures, and the workability at room temperature is not impaired at all.

Because of the non-flowability at high temperatures, even if putty is used in the vertical through hole, it will not leak out of the through hole and fall.

(f) component-heat-resistant fiber materials; At least 200 degreeC The 1 type, or 2 or more types of what consists of organic or inorganic substance which does not soften or disperse | distribute is used.

Examples of fibrous materials of such materials include asbestos, glass wool, rock wool, carbon fiber, aluminum, iron, fibers of the same metal, polyamide, polyimide, polyamideimide, teflon ( Fibers of heat-resistant organic polymers). The fiber of the heat resistant fiber material has a thickness of 100 µm or less, particularly 0.05-20 µm, and a length of 0.5 mm-100 mm, particularly 1 mm-50 mm.

The usage-amount of (f) component is 1-100 parts per 100 parts of said (a) component, Preferably it is 5-60 parts, Especially preferably, it is 10-30 parts.

Use of the component (f) has the effect of reinforcing the putty of the present invention and improving airtightness.

(g) component-microballoon; It is formed of an organic or inorganic material and is microparticles with pores therein. The void may be closed from the atmosphere or may be opened in the atmosphere. The average particle diameter is 5-1000 µm, preferably 10-300 µm, and one or two or more of those having an elevated density (g / cc) of 0.01-0.7 and preferably 0.1-0.5. Used.

Examples of microballoons include glass balloons made of glass such as borosilicate glass and glase from Volcano (shirasu), epoxy resins, phenool resins, vinylidene chloride-acrylonitrile copolymers, and sarans ( Plastic bubble cloud and carbon bubble cloud made of synthetic resin).

The usage-amount of (g) component is 20-700 parts per 100 parts of (a) component, Preferably it is 100-500 parts, especially 200-400 parts.

Use of (g) component improves the thermal insulation effect of the foamed carbonaceous layer generated when the putty of the present invention is foamed by the flame, and greatly improves the fire resistance.

In the present invention, an excellent putty can be obtained only by using one of the above-mentioned components (c)-(g), but when two or more components are used in combination, the effect of adding each component is caustic. Is preferred.

Good example of plural component combination

(c and d), (d and e), (d and f), (d and g), (c, d and e or f or g), (c, d, e and f), (c, d , e and g), (e and f), (e and g), (c, d, e, f and g), and the like.

In this case, although the usage-amount of each component may be as shown above for each component, when c component and d component are used together, regardless of the use of (e)-(g) component, (b), ( c) and (d) the ratios of α points (60, 10, 30), β points (60, 30, 10) and γ points (30, 60, 10) on the triangular coordinates shown in the figure. , within the region surrounded by a straight line connecting the points δ (10, 60, 30), ε points (10, 30, 60), and points ζ (30, 10, 60) sequentially, more preferably A point ( 50, 30, 20), B points (20, 60, 20) and C points (20, 30, 50) in the area surrounded by a straight line connected in sequence, and (b), (c) and The total amount of the component (d) may be 200-1400 parts per 100 parts of the component (a). More preferably, 300-1100 parts, in this case, the putty which is excellent in foaming fire retardance is especially obtained.

In the present invention, in addition to the above, pigments, antioxidants, inorganic fillers, carbon black, stabilizers, flame retardants (Flame Retardancy of Polymeric Materials ® Volume 1-2 edited by WCKuryla and AJ Papa, Marcel Dekker, Inc.) New York 1973) and the like may be combined with 0.1-15 parts of 100 parts of the putty of the present invention.

The putty of the present invention can be produced by sufficiently mixing the compounding components at a temperature of room temperature of 100 ° C. using an ordinary kneader such as a Kneader, a Mixtruder, or the like.

In the putty containing only (a) and (b) components, when at least 4% by weight of (a) is present, the component (b) is 96% by weight and (b) when at least 13% by weight is present ( a) A component becomes 87 weight%. However, it is not necessary to use just 87% by weight of the component (a) or 96% by weight of the component (b).

More usually, the component (a) is about 4-60% by weight, more preferably about 5-35% by weight, whereas component (b) is generally about 13-85%, more preferably About 15-60% by weight, most preferred is about 20-50% by weight.

The case where it is more preferable than usual and the% of the most preferable case is when the said putty contains only (a) and (b) component. However, more and most preferred cases are particularly useful when the other components described herein and (a) and (b) are present in admixture.

The putty of the present invention is effective not only by being applied to various through holes, teeth, etc., but also by the method of coating the surface of a fire prevention facility. Usually, the penetrating part of the electric wire cable is often extended and opened. The putty of the present invention is non-hardened, so even in such a construction, it can be easily removed and reused. Do.

Next, the comparison of the conventional fire prevention method and the fire performance of the putty of this invention is shown by experiment 1-4. Experiment 1-3 is a conventional fire prevention method, and experiment 4 is a case where the putty of this invention is used.

[Experiment 1]

A 150mm diameter through hole installed on a 100mm thick concrete wall was made to pass through 600V insulated and Polyvinyl chloride Sheathed 3cx 3.5mm2 (outer diameter of about 13.5mm) through 10 holes. The steel plate of thickness 3mm was sealed using the bolt. Next, one of the wire cable through portions was held at a temperature of 700 to 800 ° C. for 1 hour using a propane gas burner.

After 1-2 minutes of heating, smoke began to penetrate on the other side of the penetration, exposed after 30-40 minutes, and significant permeation was observed, and after 50 minutes burned to the wire not heated by burner. Could see.

[Experiment 2]

The experiment was different from Comparative Example 1 only in that the pores in the through-holes were sealed with a glass wool having a filling density of 0.4 g / cc in place of the steel plate sealing.

As a result, permeation of smoke was observed after 1-2 minutes, and the amount was significantly increased after 20-30 minutes.

[Experiment 3]

A compound consisting of 100 parts of polybutene (Viscosity at 210 ° F. 17 c.St.) and 400 parts of ammonium polyphosphate was replaced with the glass surface of Comparative Example 2, and charged. As a result, about 20 minutes later, the permeation | transmission of the smoke was recognized remarkably, and the combustion of the considerable amount was generate | occur | produced in the electric wire on the side which is not heated by burner.

[Experiment 4]

The putty of Example 8 shown in the following table was replaced with the compound of Comparative Example 3 and filled and subjected to the same test. As a result, after 50 minutes, the permeation of minute smoke was recognized as rain, but at that time, the wire on the side not yet heated by the burner was intact.

Example 1-21

Putty of the various examples shown in the 1st table | surface was manufactured by stirring for 10 minutes at the temperature of 80 degreeC, using 1 k of capacity | capacitances and 2 kneaders of stirring blades. The putty of each Example was evaluated by kneading workability, foaming fire resistance, moisture resistance, and heat resistance by the test method described later, and the results are shown in the first table.

TABLE 1

(Note 1) Conical penetration 230 (JIS K2560)

Dropping Point 200 ℃ or higher (JIS K2561)

(Note 2) Conical penetration 125 (JIS K2560)

Dropping Point 200 ℃ or higher (JIS K2561)

(Note 3) Thickness 0.07㎛ 3mm in length

(Note 4) Thickness 13㎛ 13mm in length

(Note 5) Average particle size 200-300㎛ apparent density 0.24 (g / cc)

(Note 6) Average particle size 20-80㎛ apparent density 0.21 (g / cc)

(A) component, (b) component, (c) component, (d) component, (e) component, in a test kneader of 1 L of mixing workability and two stirring blades f) Add appropriate amounts of components and (g) components respectively, stir for 10 minutes at room temperature at 80 ° C, and judge them in three steps: right, quantity, and inadmissibility by visually contacting the finished state of the finished mixture. .

[Fire proof test]

600V3c × 3.5mm2 (outer diameter of 13.5mm) Insulated cable (crosslinked polyethylene insulated and polyvinyl chloride sheath) In a 30 cm jimpum, putty is coated with a thickness of about 3 mm to make a sample. In order to measure the temperature directly under the coating at the time of the combustion test, a thermocouple is inserted between the core and the coating where the flame touches.

The sample is burned by Bunsen Burner temperature controlled to a flame temperature of 1100-1200 ° C.

Immediately after the sample is in contact with the flame, measure the time until the voltage is shorted by overcharging the AC600V voltage between the lines.

On the other hand, the temperature of the coating inner surface of the center part in contact with the flame is continuously recorded with the thermocouple inserted in advance.

Test results were divided into five stages based on the criteria described below.

That is, the short-circuit time in AC600V overcharge is 40 minutes or more, and the time when the temperature of the inner surface which the flame center part touches rises to 400 degreeC is 30 minutes or more. It is possible to have a water shortage with a short circuit time of 30 minutes or more, a temperature rise time of 10 minutes or more, a short circuit time of 10 minutes or more, and a temperature rise time of 10 minutes or more. It was determined that the short-circuit time was 4 minutes or more, and that the temperature rise time was 4 minutes or more, and that the short-circuit time was less than 4 minutes and the temperature rise time was less than 3 minutes.

[Moisture proof test]

The sample wire having a length of about 30 cm made in the same manner as the foam fire protection was left for 7 days in a sealed state in a constant temperature and humidity bath adjusted to a relative temperature of 90% at 40 ° C., and then taken out. The foaming fire protection performance was investigated in accordance with the performance evaluation test method, and the moisture resistance was shown according to the criterion shown in the second table.

[Table 2]

[Heat aging test]

A sample wire having a length of about 30 cm made in the same manner as for the genital foam fire resistance test was taken out in a geared oven controlled at 70 ° C. for 30 days, and then taken out of the foam fire protection test. In accordance with the criterion indicated in Table 2, the heat resistance was shown over time.

[Confidentiality Test]

One end of the iron pipe 300 mm in inner diameter and 600 mm in length was filled with a thickness of 100 mm in the above embodiment, and the surface of the putty was exposed to atmospheric pressure in an atmosphere of room temperature, and 0.8 kg / cm 2 gauge pressure was applied to the other end of the pipe. The air pressure is applied for 5 minutes, and the leakage of air passing through the filling putty layer in the meantime is 5 (l / min) or less.

Claims (1)

At least 4% by weight of an organic substance which is liquid or semisolid at room temperature and has a viscosity of 50-100,000 c.st. at 210 ° F, at least 13% by weight of a nitrogen-containing phosphate compound represented by the following general formula (I), Non-volatile natural or synthetic oils and viscous pastes at room temperature made from viscous agents, as defined in JIS A5752-1966, which are composed of lubricating grease with a cone penetration of 40-500 as specified in JIS K2560-1969. A foamable fireproof putty having a cone penetration of 2-40 (mm / 150g, 5 seconds 20 ° C.) as defined in JIS A5752-1966, which is composed of lubricating grease having a cone penetration of 40-500.

Where 0 <X / Y

3, n is 1-14, at least 7% by weight of the total nitrogen-containing phosphate compound is phosphorus, and at least one monovalent, 2 hydrogen atom is one or all composed of nitrogen, hydrogen and / or carbon Substituted with a valent or trivalent nitrogen containing group.

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